Production of fluorescence producing substances soluble in hydrocarbon oils



Feb. 23, 1937. HARTMANN ET AL 2,071,521

, PRODUCTION 0F FLUORESCENCE PRODUCING SUBSTANCES SOLUBLE IN HYDROCARBONOILS Filed Aug. 1l, 1932 VESSEL V533 EL F02 Co MPL/57E /PGL rfv/E22 /zA77o WA TER /NLE 7' Se PA 2A r/bfv v.s.s El.

Maw@ @www Patented Feb. 23, 1931 PATENT OFFICE PRODUCTION OFFLUORESCENCE PRO- DUCING vSUBSTANCES SOLUBLE IN HYDROCABBON OILS HansHartmann and Hans Rabe, Mannheim,

Germany, assignors Aktiengesellschaft,

Germany to I. G. Farhenindustrie Frankforton -the-Maln,

Application August 11, 1932, Serial No. 628,365

In Germany February 3, 1930 (Cl. ISB-78) 5 Claims.`

consistency, may be dissolved in lubricating oils while warming and havethe disadvantage that the greater part of them is precipitated again,after allowing the solution to stand and cool for some time, and that inmany cases they give only a slight opalescence. These productsfurthermore are not soluble in benzines but are precipitated by them. c

We have now found that fluorescence producing substances which arereadily soluble, even at low temperatures, in hydrocarbon oils`(by whichexpression we understand heavy oils or middle oils or lubricating oilsor liquid motor fuels, such as benzines, or' other liquid hydrocarbonfractions-Whether they be of `naphthenic or paratflnic base-) 4areobtained, if oleiines of purely aliphatic constitution, which are liquidat ordinary temperature, are subjected tdcondensation with polynuclearorganic -substances in which none of the nuclei is saturated withhydrogen, said condensation being carried out at an elevated temperaturein the presence of condensing catalysts of the Friedel-Crafts-type, inparticular aluminium chloride. Of particular advantage are those of theaforesaid polynuclear substances whose aromatic nuclei are devoid ofsubstituents. Examples of such substances are unsubstituted polynucleararomatic hydrocarbons.' such as naphthalene or anthraceneorphenanthrene, or polynuclearhetero'cyclic compounds, such as carbazol.As olenes suitable as initial materials for this conversion may bementioned the liquid products obtained by cracking paraillnichydrocarbons, such as hard or vsoft parailin wax, petrolatum, or oilsentirely or mainly consisting of paramnic hydrocarbons; or oleflnesobtained by;

dehydration `of alcohols, such as from octodecyl alcohol.

The, said condensation of oleiines and polynuclear aromatic hydrocarbonsis effected at temperatures between and 250 C., preferably between and200 C. In order to carry off the great heat evolved by the saidcondensation, the

treated materials are preferably diluted with an indifferent diluent,such as, :for example, a' benzine fraction boiling between and 200 C.,or another oil boiling at the same or higher temperatures, andsimultaneously externally cooled.

plus does not take part in the reaction, but acts only as a diluent andwould have to be distilled from the resulting condensation. product. Theintensity ofthe iiuorescence caused by a deiinite amount ofthecondensation product is the greater the greater is the amount ofaluminium chloride employed.l Preferably from 20 to 60 per cent ofaluminiumchloride with reference to the amount. ofthe initial oleilnesto be condensed are employed With larger amounts oialuminium chloridethe resulting condensation products produce a uorescence having aslightly blue tinge. The products` obtained according to thepresentinvention ordinarily have a mean molecular weight of between 600and 8 00.

.The accompanying drawing shows a schematic layout of equipment suitablefor carrying out the process, and the drawing is provided withappropriate legends to equipment.

The fluorescence producing substances thus obtained are thickly liquid,viscdus products which explain the functioning of the at ordinarytemperature may be dissolved in hydrocarbon oils of naphthenic or paramnbase,

- such as in lubricating oils or in benzine. No

'precipitation or resiniflcation occurs in the oils mixed with the saidsubstances. 'I'he oils conrtaining these substances are" entirely clearin transparent light. An addition of from 0.1 to 0.2 per cent issumcient for imparting to the oil a red colrin transmitted light andagreen color in reilected light, so that this'oil, in its appearance, isinl no way different from that of a Pennsylvanian oil. Th'e followingexamples will further illustrate how the present invention may becarried out in practice; the invention is, however, not restricted tothese examples.

' f Example 1 i 1 kilogram of a fraction mainly consisting of oleilneswhich boils between 90 and 150 C under a pressure 012 millimetersmercury gauge and which has been obtained by cracking soft.

paraiiin wax is subjected to condensation with 1,

kilogram of naphthalene in the presence of 0.4 kilogram af aluminiumchloride. The reaction product having attained a temperature of 180 C..is allowed to cool down, then stirred with water and thereupon freedfrom the solid matter mainly consisting of the aluminium hydroxideformed. 'I'he reaction product is then heated to 150 C. under a pressureof 2 millimeters mercury gauge, 0.05 kilogram of oil thereby beingdistilled as iirst runnings. The liquid residue amounting to 1.9kilograms represents an excellent fluorescence producing substancesoluble in lubricating oils and benzine. If a mineral oil having ayellow color is mixed with 0.15 per cent of its Weight of the saidliquid residue the mineral oil obtains a. remarkable green fluorescenceand appears red in transmitted light.

' Example 2 4 kilograms of a product obtained by cracking petrolatum,which boils above 100 C. under a pressure of 2 millimeters mercury-gaugeare polymer-ized with 1 kilogram of naphthalene, 0.5 kilogram ofanthracene oil and 0.5 kilogram of carbazol in the presence of 1.2kilograms of aluminium chloride at a temperature of 200 C. whilestirring. The resulting products are worked up as described inExample 1. An oil is thus obtained in a nearly quantitative yieldrepresenting a iiuorescence producing substance which when added to anoil causes that the latter appears red in transmitted light and green inreected light.

Example 3 10 kilograms of a product obtained by 'crack- 1 ing hardparailin wax and which boils between 20 and 300 C. at atmosphericpressure is diluted with 5 kilograms of rst runnings as obtained forexample in the process described in Examplel 1. After adding 6 kilogramsof naphthalene and 10 kilograms of aluminium chloridel to the mixturethe whole is` polymerized for 2 hours at about 125 C. Theresultingproduct is worked up as described in Example 1. In addition to 6kilograms of rst runnings 14.5 kilograms of a viscous product areobtained which when added to an oil showing no fluorescence in an amountof 0.2 per cent of the amount of oil, imparts to the oil a iluorescencewhich is in no way diilerent from that of a Pennsylvanian oil.

Example 4 20 kilograms of a product obtained by cracking paraflin waxwhich has been diluted with 8 kilograms of a high boiling benzinefraction, are mixed with 5 kilograms of naphthalene and 7.5 kilograms ofaluminium chloride added to the mixture in 3 portions amounting each to2.5 kilograms, the second and third portions being added only after thereaction set up by the last preceding portion is nished (which mayeasily be determined by the decrease of the tempera'- ture). The wholeof the aluminium chloride having been added to the reaction mixture, thelatter is maintained for about 1 hour at 150 C. The reaction product,when worked up as described in Example 1 represents a uorescenceproducing substance which when added to an oil in an amount vof 0.1 percent imparts to the latter a green uorescence and a red appearance intransmitted light.

Example 5 10 kilograms of a product obtained by cracking paraiiin waxare diluted with 10 kilograms of rst runnings as obtained for example inthe process described in Example 1 and,4 after an addition of 5kilograms of aluminium chloride, polymerized while simultaneouslyintroducing the cracking gases obtained in the cracking of paraffin wax.After the reaction temperature E has attained about C., 8 kilograms ofnaph` thalene, 1 kilogram of anthracene and 0.5 kilogram of phenanthreneare added. The Whole mixture is then heated to 150 C, and maintained atthis temperature for one hour. The resulting products are subjected todistillation at 150 C. under a pressure of 1 millimeter mercury gauge,18 kilograms of a substance vbeing obtained as residue which when addedto oils imparts to them a fluorescence as intensive as do the productsobtained as described in the foregoing examples. v

The addition of the said cracking gases does not materially increase theyield of the uorescence producing substance but the amount of theportions which are separated by the distillation Vof the condensationproducts and which constitute oils having lubricating properties isconsiderably increased. In this manner the cracking gases are made useof at the same time for the preparation of lubricating oils.

In the appended claims by the term condensation (or condensing) it isintended to include both condensation and polymerization.

1. A process for the production of a uorescence producing substancewhich is soluble in hydrocarbon oils which comprises subjecting amixture of an oleiine of purely aliphatic constitution and liquid atordinary room temperature with from 20 to 70 per cent with reference tosaid oleiine of a polynuclear aromatic'substance in which none of thenuclei is saturated with hydrogen to condensation at a temperaturebetween '70 and 250 C. and in the presence of at least 20% withreference to said olei'ine of a condensing agent of the Friedel-Craftstype for a reaction time such as to produce uorescence producingsubstances, soluble in hydrocarbon oils, and having a mean molecularweight of between 600 and 800.

2. A process for the production of a fluorescence producing substancewhich is soluble in hydrocarbon oils which comprises subjecting amixture of an olene of purely aliphatic constitution and liquid atordinary room temperature with from 20 to :70 per cent with reference tosaid olefine of a polynuclear aromatic substance in which none of thenuclei is saturated with hydrogen to condensation at a temperaturebetween and 200 C. and in the presence of at least 20% with reference tosaid olene of a condensing agent of the Friedel-Crafts type for areaction time such as to produce fluorescence producing substances,soluble in hydrocarbon oils, and having a mean molecular weight ofbetween 600 and 800.

3. A process for the production of a uorescence producing substancewhich is soluble in hydrocarbon oils which comprises subjecting amixture of a liquid at least mainly consisting of olenes liquid atordinary temperature, which is obtained by cracking parain wax with from20 to 70 per cent, with reference to the olefines contained in saidliquid of naphthalene to condensation at a temperature between 70 and250 C. and in the presence of at least 20% with reference to saidolefln'e of aluminium chloride rescence producing substances,

as to produce uosoluble in hydrocarbon oils, and having a mean molecularweight of between 600 and 800.

4. A process for the for a reaction time such production o! a. uo

i rescence producing substance which is soluble in hydrocarbon oilswhich comprises subjecting a mixture of a liquid consisting at leastmainly of oleiines of purely aliphatic constitution and liquid atordinary room temperature with from 20 to '70 per cent with reference tothe olenes contained in said liquid of a polynuclear aromatic substancein which none ot the nuclei is saturated with hydrogen and which isdevoid of substituents to condensation at a temperature between 70 and250 C. and in the presence of from 20 to 60 per cent by weight oi saidmix= ture of #um chloride for a reaction time hydrocarbon oils,

such as to produce iiuorescence producing substances, soluble inhydrocarbon oils, and having,

a mean molecular weight of between 600 and 800.

5. A process for the production of a iiuorescence producing substancewhich is soluble in which comprises subjectingr a mixture of a liquidoleilne of purely aliphatic constitution with more than 20 per cent withreference to said olene of a polynuclear aromatic substance in whichnone of the nuclei is saturated with hydrogen, to condensation at acondensing temperature 'and in the presence of at least 20% withreference to said olene of a condensing agent of the Friedel-Craftstype.

